The present invention relates to a chemical amplifying type positive resist composition used in the minute processing of a semiconductor.
A lithography process using a resist composition has usually been adopted in the minute processing of a semiconductor. In the lithography, the resolution can be improved with a decrease in wavelength of exposure light in principle as expressed by the equation of Rayleigh""s diffraction limit. A g-line with a wavelength of 436 nm, an i-line with a wavelength of 365 nm, and a KrF excimer laser with a wavelength of 248 nm have been adopted as exposure light sources for lithography used in the manufacture of a semiconductor. Thus, the wavelength has become shorter year by year. An ArF excimer laser having a wavelength of 193 nm is considered to be promising as a next-generation exposure light source.
A lens used in an ArF excimer laser exposure machine has a shorter lifetime as compared with lenses for conventional exposure light sources. Accordingly, the shorter time required for exposure to ArF excimer laser light is desirable. For this reason, it is necessary to enhance the sensitivity of a resist. Consequently, there has been used a so-called chemical amplifying type resist, which utilizes the catalytic action of an acid generated by exposure and contains a resin having a group cleavable by the acid.
It is known that, desirably, resins used in a resist for ArF excimer laser exposure have no aromatic ring in order to ensure the transmittance of the resist, but have an alicyclic ring in place of an aromatic ring in order to impart a dry etching resistance thereto. Various kinds of resins such as those described in Journal of Photopolymer Science and Technology, Vol. 9, No. 3, pages 387-398 (1996) by D. C. Hofer, are heretofore known as such resins.
As a resin used in a resist for ArF excimer laser exposure, a mutual copolymer composed of a polymerization unit of alicyclic olefin and a polymerization unit of an unsaturated dicarboxylic acid anhydride (T. I. Wallow et al., Proc. SPIE, vol. 2724, pp. 355-364 (1996)), a polymer having an alicycliclactone structure unit (JP-A-2000-26446) and the like are known. However, any of such resins finds difficulty in providing dry etching resistance as high as that of an aromatic ring.
An object of the present invention is to provide a chemical amplifying type positive resist composition comprising a resin and an acid generating agent suitable for lithography using excimer laser light such as ArF and KrF, which is excellent in balance of performance of resolution and sensitivity and has high dry etching resistance.
The present inventors have found that a resist composition excellent in balance of performance such as resolution, profile, sensitivity and adhesion and high in dry etching resistance is obtainable by using a resin having a polymerization unit derived from a monomer having a specific structure, as a part of the polymerization units of a resin constituting a chemical amplifying type positive resist composition. The present invention has been completed based on this finding.
The present invention provides a chemical amplifying type positive resist composition comprising;
a resin having a polymerization unit derived from a monomer represented by the following formula (I): 
wherein R1 and R2 independently represent hydrogen or an alkyl group having 1 to 4 carbons, and R3 represents hydrogen or a methyl group;
the resin being insoluble in alkali itself but becoming alkali-soluble die to the action of an acid; and
an acid generating agent.
The resist composition of the present invention comprises a resin having a polymerization unit derived from a monomer represented by the formula (I) above as a resin component. Specific examples of the monomer represented by formula (I) include the following compounds with the one on the left being preferable. 
The resin as a component of the positive resist composition of the present invention is insoluble in alkali but becomes soluble due to the action of an acid. The resin preferably contains a polymerization unit having a group deblocked due to the action of an acid.
Specific examples of the group deblocked due to the action of an acid include various types of carboxylic acid esters, including: alkyl esters having about 1 to 6 carbons typified by tert-butyl ester; acetal esters such as methoxymethyl ester, ethoxymethyl ester, 1-ethoxyethyl ester, 1-isobutoxyethyl ester, 1-isopropoxyethyl ester, 1-ethoxypropyl ester, 1-(2-methoxyethoxy)ethyl ester, 1-(2-acetoxyethoxy)ethyl ester, 1-[2-(1-adamantyloxy)ethoxy]ethyl ester, 1-[2-(1-adamantanecarbonyloxy)ethoxy]ethyl ester, tetrahydro-2-furyl ester and tetrahydro-2-pyranyl ester; and alicyclic esters such as 2-alkyl-2-adamantyl, 1-(1-adamantyl)-1-alkylalkyl and isobornyl ester.
The monomer from which the polymerization unit having a carboxylic acid ester described above is derived may be an acrylic one such as methacrylic acid ester and acrylic acid ester, or an alicyclic monomer with a carboxylic ester group bound thereto, such as norbornene carboxylic acid ester, tricyclodecene carboxylic acid ester and tetracyclodecene carboxylic acid ester. Otherwise, it may be an ester formed by an alicyclic group of an alicyclic carboxylic acid ester and an acrylic acid or a methacrylic acid, as described in Iwasa et al., Journal of Photopolymer Science and Technology, Vol. 9, No. 3, pp. 447-456 (1996).
Among the monomers described above, one having a bulky group containing an alicyclic group such as 2-alkyl-2-adamantyl and 1-(1-adamantyl)-1-alkylalkyl, as the group deblocked due to the action of an acid, is preferably used because such a monomer exhibits excellent resolution. Examples of the monomer having a bulky group containing an alicyclic group include (meta)acrylic acid 2-alkyl-2-adamantyl, (meta)acrylic acid 1-(1-adamantyl)-1-alkylalkyl, 5-norbornene-2-carboxylic acid 2-alkyl-2-adamantyl and 5-norbornene-2-carboxylic acid 1-(1-adamantyl)-1-alkylalkyl.
Among others, use of (meta)acrylic acid 2-alkyl-2-adamantyl as the monomer is preferred for its excellent resolution. Typical examples of the (meta)acrylic acid 2-alkyl-2-adamantyl include acrylic acid 2-methyl-2-adamantyl, methacrylic acid 2-methyl-2-adamantyl, acrylic acid 2-ethyl-2-adamantyl, methacrylic acid 2-ethyl-2-adamantyl and acrylic acid 2-n butyl-2-adamantyl. Among others, acrylic acid 2-methyl-2-adamantyl and methacrylic acid 2-methyl-2-adamantyl are preferred.
Another monomer having a group deblocked due to the action of an acid may also be used as required.
The resin according to the present invention may also have a polymerization unit derived from a monomer having no group deblocked due to the action of an acid. Examples of such a monomer include (meta)acrylic acid esters, alicyclic olefins, unsaturated dicarboxylic acid anhydrides and (meta)acrylonitrile. Specifically, the following compounds are included:
3-hydroxy-1-adamantyl acrylate;
3-hydroxy-1-adamantyl methacrylate;
3,5-dihydroxy-1-adamantyl methacrylate;
xcex1-acryloyloxy-xcex3-butyrolactone;
xcex1-methacryloyloxy-xcex3-butyrolactone;
xcex2-acryloyloxy-xcex3-butyrolactone;
xcex2-methacryloyloxy-xcex3-butyrolactone;
5-acryloyloxy-2,6-norbornane carbolactone;
5-methacryloyloxy-2,6-norbornane carbolactone;
2-norbornen;
2-hydroxy-5-norbornen;
5-norbornen-2-carboxylate;
methyl 5-norbornen-2-carboxylate;
5-norbornen-2-carboxylate-t-butyl
1-cyclohexyl-1-methylethyl 5-norbornen-2-carboxylate;
1-(4-methylcyclohexyl)-1-methylethyl 5-norbornen-2-carboxylate;
1-(4-hydroxycyclohexyl)-1-methylethyl 5-norbornen-2-carboxylate;
1-methyl-1-(4-oxocyclohexyl)ethyl 5-norbornen-2-carboxylate;
1-(1-adamantyl)-1-methylethyl 5-norbornen-2-carboxylate;
1-methylcyclohexyl 5-norbornen-2-carboxylate;
2-methyl-2-adamantyl 5-norbornen-2-carboxylate;
2-ethyl-2-adamantyl 5-norbornen-2-carboxylate;
2-hydroxy-1-ethyl 5-norbornen-2-carboxylate;
5-norbornen-2-methanol;
5-norbornen-2,3-dicarboxylic acid anhydride; etc.;
maleic anhydride; and
itaconic anhydride.
A resin used in the present invention varies depending on the type of rays used in the exposure for patterning, the types of other polymerization units contained as required, etc., but it is preferably obtained by polymerizing 5 to 50 mol % of a monomer expressed by the formula (1) with any other monomers as required.
The copolymerization can be carried out by a normal method. For example, a copolymer resin specified in the present invention can be obtained by dissolving the required monomers in an organic solvent and polymerizing the same in the presence of a polymerization initiator like an azo compound such as 2,2xe2x80x2-azo-bisisobutyronitrile or dimethyl 2,2xe2x80x2azobis(2-methylpropionate). After the reaction, it is advantageous to purify the same by reprecipitation.
The acid generating agent, another component of the resist composition, is a substance which is decomposed to generate an acid by applying a radiation such as a light, an electron beam or the like on the substance itself or on a resist composition containing the substance. The acid generated from the acid generating agent acts on said resin resulting in cleavage of the group cleavable by the action of an acid existing in the resin.
Such acid generating agents, for example, include other onium salt compounds, organno-halogen compound, sulfone compounds, sulfonate compounds, and the like.
Specific examples thereof include:
diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate,
4-mthoxyphenylphenyliodonium trifluoromethanesulfonate,
bis(4-tert-butylphenyl)iodonium tetrafluoroborate,
bis(4-tert-butylphenyl)iodonium hexafluorophosphate,
bis(4-tert-butylphenyl)iodonium hexafluoroantimonate,
bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate,
bis(4-tert-butylphenyl)iodonium camphorsulfonate,
triphenyisulfonium hexafluorophosphate,
triphenylsulfonium hexafluoroantimonate,
triphenylsulfonium trifluoromethanesulfonate,
4-methoxyphenyldiphenylsulfonium hexafluoroantimonate,
4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate,
p-tolyldiphenylsulfonium trifluoromethanesulfonate,
p-tolyldiphenylsulfonium perfluorobutanesulfonate,
p-tolyldiphenylsulfonium perfluorooctanesulfonate,
2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate,
4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate,
4-phenylthiophenyldiphenylsulfonium hexafluorophosphate,
4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate,
1-(2-naphthoylmethyl)thiolanium hexafluoroantimonate,
1-(2-naphthoylmethyl)thiolanium trifluoromethanesulfonate,
4-hydroxy-1-naphthyldimethylsulfonium hexafluoroantimonate,
4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate,
cyclohexylmethyl(2-oxocyclohexyl)sulfonium trifluoromethanesulfonate,
cyclohexylmethyl(2-oxocyclohexyl)sulfonium perfluorobutanesulfonate,
cyclohexylmethyl(2-oxocyclohexyl)sulfonium perfluorooctanesulfonate,
2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine,
2,4,6-tris(trichloromethyl)-1,3,5-triazine,
2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
2-(4-pentyloxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine,
diphenyl disulfone,
di-p-tolyl disulfone,
bis(phenylsulfonyl)diazomethane,
bis(p-tolylsulfonyl)diazomethane,
bis(4-tert-butylphenylsulfonyl)diazomethane,
bis(2,4-xylylsulfonyl)diazomethane,
bis(cyclohexylsulfonyl)diazomethane,
(benzoyl)(phenylsulfonyl)diazomethane,
1-benzoyl-1-phenylmethyl p-toluenesulfonate (so-called benzointosylate),
2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonate (so-called xcex1-methylolbenzointosylate),
1,2,3-benzenetriyl trimethanesulfonate,
2,6-dinitrobenzyl p-toluenesulfonate,
2-nitrobenzyl p-toluenesulfonate,
4-nitrobenzyl p-toluenesulfonate,
N-(phenylsulfonyloxy)succinimide,
N-(trifluoromethylsulfonyloxy)succinimide,
N-(trifluoromethylsulfonyloxy)phthalimide,
N-(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxyimide,
N-(trifluoromethylsulfonyloxy)naphthalimide,
N-(10-camphorsulfonyloxy)naphthalimide, and the like.
It is also known that, generally in a chemical amplifying type positive resist composition, performance deterioration due to the deactivation of an acid associated with leaving after exposure can be reduced by adding basic compounds, especially basic nitrogen-containing organic compounds such as amines as quenchers. It is also preferable in the present invention that such basic compounds are added. Concrete examples of the basic compounds to be used as quenchers include the ones represented by the following formulae: 
wherein R11, R12 and R17 represent, independently each other, hydrogen, cycloalkyl, aryl or alkyl which may be optionally substituted with a hydroxyl, amino which may be optionally substituted with alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; R13, R14 and R15, which are same or different from each other, represent hydrogen, cycloalkyl, aryl, alkoxy or alkyl which may be optionally substituted with a hydroxyl, amino which may be optionally substituted with alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; R16 represents cycloalkyl or alkyl which may be optionally substituted with a hydroxyl, amino which may be optionally substituted with alkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; A represents alkylene, carbonyl, imino, sulfide or disulfide. The alkyl represented by R11 to R17 and alkoxy represented by R13 to R15 may have about 1 to 6 carbon atoms. The cycloalkyl represented by R11 to R17 may have about 5 to 10 carbon atoms and the aryl represented by R11 to R15 and R17 may have about 6 to 10 carbon atoms. The alkylene represented by A may have about 1 to 6 carbon atoms and may be straight-chained or branched.
The resist composition of the present invention preferably contains the resin in an amount of 80 to 99.9% by weight, and the acid generating agent in an amount of 0.1 to 20% by weight based on the total weight of the resin and the acid generating agent. When a basic compound is used as a quencher, it is preferably contained in an amount in the range of 0.001 to 1 part by weight, more preferably 0.01 to 0.3 part by weight per 100 parts by weight of the resin. The composition may also contain, if required, a small amount of various additives such as sensitizers, dissolution inhibitors, resins other than the above resin, surfactants, stabilizers, and dyes so far as the objects of the present invention is not harmed.
The resist composition of the present invention generally becomes a resist solution in the state in which the above-described components are dissolved in a solvent to be applied on a substrate such as a silicon wafer. The solvent herein used may be one which dissolves each component, has an appropriate drying rate, and provides a uniform and smooth coating after evaporation of the solvent, and can be one which is generally used in this field.
Examples thereof include glycol ether esters such as ethylcellosolve acetate, methylcellosolve acetate, and propylene glycol monomethyl ether acetate; esters such as ethyl lactate, butyl acetate, amyl acetate, and ethyl pyruvate; ketones such as acetone, methyl isobutyl ketone, 2-heptanone, and cyclohexanone; and cyclic esters such as xcex3-butyrolactone. These solvents can be used alone or in combination of two or more thereof.
The resist film applied on a substrate, and dried is subjected to an exposure treatment for patterning. Then, after a heat-treatment for promoting a protecting deblocking reaction, development by an alkali developer is conducted. The alkali developer herein used can be various kinds of alkaline aqueous solutions used in this field. In general, an aqueous solution of tetramethylammoniumhydroxide or (2-hydroxyethyl)trimethylammoniumhydroxide (so-called) colline) is often used.
The present invention will be described in more detail by way of examples, which should not be construed as limiting the scope of the present invention. All parts in examples are by weight unless otherwise stated. The weight-average molecular weight is a value determined from gel permeation chromatography using polystyrene as a reference standard.